Biaxially oriented ink receptive medium

ABSTRACT

The invention provides an image receptor medium which includes a biaxially oriented, melt-processed image receptive film comprising a) an immiscible blend of at least one semicrystalline polymer component and at least one ink absorptive polymer component and b) at least one inorganic filler. The image receptor medium may further include one or more additional layers such as support or adhesive layers.

This application is a divisional of U.S. Ser. No. 10/176,556, filed Jun.21, 2002, issued as U.S. Pat. No. 6,790,491, the disclosure of which isherein incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to films that are receptive tosolvent-based inkjet inks and methods of printing onto such films. Morespecifically, the present invention relates to melt-processed films thatare receptive to solvent-based inkjet inks and methods of printing ontosuch films. A variety of polymeric sheets may be prepared includingvarious sheeting for signage and graphic films for advertising andpromotional displays.

BACKGROUND OF INVENTION

A variety of print methods have been employed for imaging various sheetmaterials. Commonly employed print methods include gravure, off-set,flexographic, lithographic, electrographic, electrophotographic(including laser printing and xerography), ion deposition (also referredto as electron beam imaging (EBI)), magnetographics, inkjet printing,screen printing, and thermal mass transfer. More detailed informationconcerning such methods is available in standard printing textbooks.

One of ordinary skill in the art appreciates the differences in thesevarious print methods and recognizes that a combination of ink andreceiving substrate that results in high image quality in one printingmethod often exhibits an entirely different image quality with anotherprint method. For example, in contact printing methods such asscreen-printing, a blade forces the ink to advance and wet the receivingsubstrate. Image defects are typically due to a subsequent recession ofthe ink contact angle with the substrate. In the case of non-contactprinting methods, such as inkjet printing, the individual ink drops aremerely deposited on the surface. In order to achieve good image quality,the ink drops need to spread, join together, and form a substantiallyuniform, leveled film. This process requires a low advancing contactangle between the ink and the substrate. For any given ink/substratecombination, the advancing contact angle is typically significantlygreater than the receding contact angle. Accordingly, ink/substratecombinations that result in good image quality when printed with contactmethods such as screen printing, often exhibit insufficient wetting whenimaged with non-contact printing methods such as inkjet printing.Insufficient wetting results in low radial diffusion of the individualink drops on the surface of the substrate (also referred to as “dotgain”), low color density, and banding effects (e.g., gaps between rowsof drops).

Another important difference between screen-printing and inkjet printingis the physical properties of the ink. Screen printing ink compositionstypically contain over 40% solids and have a viscosity of at least twoorders of magnitude greater than the viscosity of inkjet printing inks.It is not generally feasible to dilute a screen printing ink to make itsuitable for inkjet printing. The addition of large amounts of lowviscosity diluents drastically deteriorates the ink performance andproperties, particularly the durability. Further, the polymers employedin screen printing inks are typically high in molecular weight andexhibit significant elasticity. In contrast, inkjet ink compositions aretypically Newtonian.

Inkjet printing is emerging as the digital printing method of choice dueto its good resolution, flexibility, high speed, and affordability.Inkjet printers operate by ejecting, onto a receiving substrate,controlled patterns of closely spaced ink droplets. By selectivelyregulating the pattern of ink droplets, inkjet printers can produce awide variety of printed features, including text, graphics, holograms,and the like. The inks most commonly used in inkjet printers arewater-based or solvent-based. Water-based inks require porous substratesor substrates with special coatings that absorb water.

SUMMARY OF THE INVENTION

In one aspect, the invention provides an image receptor mediumcomprising a porous, voided, melt-processed image receptive film layercomprising a) an immiscible blend of a semicrystalline polymer componentand at least one ink absorptive polymer component and b) at least oneinorganic filler. The image receptor medium may further comprise one ormore additional layers such support or adhesive layers. The imagereceptor medium is a suitable substrate for non-contact ink-jet printingmethods, and is also useful for contact printing methods. The presentinvention provides an image receptor medium having good color density,as measured by densitometry, and good resolution, particularly two colorresolution, as measured by printing rows of parallel lines ofalternating colors, the lines of the first color printed at 400% ink laydown (i.e. four passes by an ink-jet printer) and the lines of thesecond color being printed at 200% ink lay down, each line being printedat one-fiftieth of an inch thickness, and the lines are readily resolvedby eye and do not bleed together. As used herein “ink lay down” meansthe amount of ink delivered to the surface of a substrate per unit ofline length.

The ink absorptive polymer component may be selected using an InclinedInk Trail test. Briefly, the test value is the ratio of the distancetraveled by an ink droplet on an inclined test substrate to that of apoly(vinyl chloride) substrate. In this test, a film of a candidate inkabsorptive polymer is mounted on an inclined substrate, an ink droplet,typically 10 microliters, is applied to it and the distance the dropletruns down the inclined surface is measured. This measured distance isthen compared to the distance measured on a control poly(vinyl chloride)substrate. Useful ink absorptive polymer components are defined by theequation:IT#=Y/X=0.75 to 2.0,Where “IT#” is the inclined ink test value, X is the distance traveledby a droplet on an inclined poly(vinyl chloride) substrate and Y is thedistance traveled on the candidate ink absorptive polymer componentsubstrate.

It has been found if the inclined ink test value is less than 0.75, thenthe color density of the ultimate image receptive medium is poor, as aresult of the solvent of the ink being absorbed too quickly. Conversely,if the inclined ink test value is greater than 2.0, the resolution ofthe ultimate image receptive medium is poor, as result of the inkabsorptive polymer having no affinity for the solvent of the ink.Preferably, the inclined ink test value will be 0.9 to 1.25.

It will be understood with respect to the above description thatcandidate ink absorptive polymer components are tested using the inksspecified for a particular printing process, and that depending on theinks employed, different ink absorptive polymer components may beselected. For example, in an ink jet printing process, ink jet printinginks would be used in evaluating candidate ink absorptive polymercomponents. Further, ink absorptive polymer components comprising blendsof polymers may also be tested using the Inclined Ink Trail Test.

Although many poly(vinyl chloride) films may be used as a control inevaluating candidate ink absorptive polymer components, it has beenfound that the differences in the test results, i.e the X value, aregenerally minor, varying less than 10% between different commerciallyavailable films. One useful control film is 3M 180-10 Commercial Graphicvinyl film, available from the 3M Company. Another useful control filmis MPI 1005 vinyl film, available from Avery-Dennison Graphics Div.,Additional details on the Inclined Ink Trail Test are provided in theexperimental section.

Many useful ink absorptive polymer components have a HildebrandSolubility Parameter of said absorptive additive within about 3.1(MPa)^(1/2) of the solvent of the ink, wherein the image receptive layerhas an ink solvent absorption of at least 50% greater than a film ofsemicrystalline polymer component alone.

In another aspect, the invention further comprises an image receptormedium comprising biaxially oriented, melt-processed image receptivefilm comprising a) at least one immiscible blend of a semicrystallinepolymer component, an ink absorptive polymer component and b) at leastone inorganic filler. The ink absorptive polymer component is, forexample, an ethylene vinyl acetate carbon monoxide terpolymer. The imagereceptor medium of such a construction may further comprise one or moreadditional layers such as support or adhesive layers.

In another aspect, the invention provides a method of printing with aninkjet printer comprising the step of jetting a solvent-based inkjet inkonto an image receptor medium comprising a biaxially oriented,melt-processed image receptive layer comprising a) an immiscible blendof a semicrystalline polymer component and an ink absorptive polymercomponent and b) an inorganic filler.

In yet another aspect, the invention provides an imaged ink receptormedia comprising an image receptive layer of the invention having animage printed thereon. The articles of the invention are useful as anintermediate or as a finished product for signage and graphic films.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a digital image of a scanning electron micrograph (SEM) of thesurface of the ink-receptive article of Example 1.

FIG. 2 is a digital image of a cross section of the image receptormedium of Example 1.

FIG. 3 is a digital image of a scanning electron micrograph (SEM) of thesurface of the ink-receptive article of Example 10.

FIG. 4 is a digital image of a scanning electron micrograph (SEM) of thesurface of the ink-receptive article of Example 11.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the invention provides an image receptor mediumcomprising a single extrudable image receptive film layer. The imagereceptive layer is a layer that is receptive to solvent-based inkjetink. “Solvent-based” means non-aqueous. The image receptive mediumcomprises a) an immiscible blend of a semicrystalline polymer component,an ink absorptive polymer component and b) an inorganic filler. In oneembodiment, the image receptor medium comprises an optional supportlayer having two major surfaces and an image receptive layer bonded,adhered or otherwise affixed to the support layer. Optionally, themedium may further comprise an adhesive layer for affixing the medium toanother substrate.

Semicrystalline polymers useful as the first polymer component in theimmiscible mixture include any melt-processible crystalline,semicrystalline or crystallizable polymers or copolymers, includingblock, graft and random copolymers. Semicrystalline polymers consist ofa mixture of amorphous regions and crystalline regions. The crystallineregions are more ordered and segments of the chains pack in crystallinelattices. If crystalline regions are heated above the meltingtemperature of the polymer, the molecules become less ordered or morerandom. If cooled rapidly, this less ordered feature is “frozen” inplace and the resulting polymer is said to be amorphous. If cooledslowly, these molecules can repack to form crystalline regions and thepolymer is said to be semicrystalline. Some polymers remain amorphousand show no tendency to crystallize. Some polymers can be madesemicrystalline by heat treatments, stretching or orienting and bysolvent inducement, and these processes can control the degree ofcrystallinity.

Semicrystalline polymers useful in the present invention include, butare not limited to, high and low density polyethylene, linear lowdensity polyethylene, polypropylene, polyoxymethylene, poly(methylpentene), poly(ethylene terephthalate), poly(butylene terephthalate),polybutene, and syndiotactic polystyrene.

The semicrystalline polymer component may further comprise small amountsof a compatible second polymer to impart desired properties to thereceptive medium of the invention. The second polymer of such blends maybe semicrystalline or amorphous and are used in amounts so that themixture remains immiscible with the solvent absorptive polymer. Thesecond polymer is generally less than 30 weight percent, based on theweight of the semicrystalline polymer component. For example, smallamounts of linear low-density polyethylene may be added topolypropylene, when used as the semicrystalline polymer component, toimprove the softness and drapability of the receptive articles. Smallamounts of other polymers may be added, for example, to enhancestiffness, crack resistance, Elmendorff tear strength, elongation,tensile strength and impact strength, as is known in the art. Theselection and amounts of any such other polymers to the semicrystallinepolymer component should not deleteriously affect the immiscibility ofthe semicrystalline polymer component and the ink absorptive polymercomponent.

Typically the semicrystalline polymer component is present in the imagereceptive medium at a level of from about 60 to about 98 weight percent,preferably 80 to about 92 weight percent, relative to the weight of theimmiscible polymer-blend. The molecular weight of the semicrystallinepolymer component should be chosen so that the polymer is meltprocessible under the processing conditions. For polypropylene andpolyethylene, for example, the molecular weight may be from about 5000to 500,000 and is preferably from about 100,000 to 300,000.

The ink absorptive polymer provides increased solvent absorbency to theimage receptive layer such that ink bleeding and running is eliminatedduring printing. By “ink absorptive” it is meant that the polymer swellsand absorbs the solvent component of the ink. Useful ink absorptivepolymers are immiscible with the semicrystalline polymer component andhave an Inclined Ink Trail Test value (IT#) of from 0.75 to 2.0. The inkabsorptive polymer component may further have a Hildebrand solubilityparameter within about 1.5 (cal/cm³)^(1/2) to (3.1 (MPa)^(1/2)) of thesolvent(s) of the ink. “Hildebrand solubility parameter” refers to asolubility parameter represented by the square root of the cohesiveenergy density of a material, having units of (pressure )^(1/2), andbeing equal to (ΔH-RT)^(1/2)V^(1/2) where ΔH is the molar vaporizationenthalpy of the material, R is the universal gas constant, T is theabsolute temperature, and V is the molar volume of the solvent.Hildebrand solubility parameters are tabulated for solvents in: Barton,A. F. M., Handbook of Solubility and Other Cohesion Parameters, 2^(nd)Ed., CRC Press, Boca Raton, Fla. (1991), for monomers and representativepolymers in Polymer Handbook, 3^(rd) Ed., J. Brandrup & E. H. Immergut,Eds. John Wiley, NY, pp 519–557 (1989), and for many commerciallyavailable polymers in Barton, A. F. M., Handbook of Polymer-LiquidInteraction Parameters and Solubility Parameters, CRC Press, Boca Raton,Fla. (1990).

Useful ink absorptive additive polymer components includepoly(meth)acrylic polymers such as PARALOID and ACRYLOID polymers fromRohm and Haas, Philadelphia, Pa., and ELVACITE polymers from IneosAcrylics, Cordova, Tenn.; vinyl polymers such as UCAR polymers fromUnion Carbide, Danbury, Conn. a subsidiary of The Dow Chemical Company;and polystyrene polymers such as STYRON polymers available from The DowChemical Company, Midland, Mich. or styrene/acrylonitrile copolymerssuch as LURAN available form BASF, Mount Olive, N.J. Othervinyl/poly(vinyl chloride) polymers are available from BF GoodrichPerformance Materials, Cleveland, Ohio, and BASF, Mount Olive. N.J.Useful (meth) acrylic polymers have a Tg of 90° C. or less.

Specific examples of useful (meth)acrylic polymers include copolymers ofmethyl methacrylate with butyl acrylate, butyl methacrylate, isobutylmethacrylate, or isobornyl methacrylate (e.g., PARALOID DM-55, PARALOIDB48N, PARALOID B66, ELVACITE 2550), copolymers of isobutylmethacrylateand butyl methacrylate (e.g., ELVACITE 2046), and isobutyl methacrylatepolymers (e.g., PARALOID B67). Specific examples of useful vinyl andpolystyrene polymers include UCAR VYHH, VMCC, and VAGH vinyl polymersavailable from Union Carbide; STYRON 478, 663, 678C, and 693 polystyrenepolymers from The Dow Chemical Company; and 145D and 148G polystyrenepolymers from BASF, Mount Olive, N.J.

The incorporation of butyl acrylate, butyl methacrylate, isobutylmethacrylate, or isobornyl methacrylate co-monomer into methylmethacrylate polymers reduces the solubility parameter of the resulting(meth)acrylic polymer such that the solubility parameter of the polymermore closely matches that of the solvent system in the inks, therebyproviding faster solvent absorption for the print receptive blend. Theincorporation of these co-monomers into (meth)acrylic polymer alsotypically reduces the glass transition temperature of the (meth)acrylicpolymer which may also facilitate solvent uptake by the image receptivelayer. Combinations of such polymers may also be used as the inkabsorptive polymer.

Generally, copolymers comprising the reaction product of olefin monomersand a sufficient amount of at least one polar monomer (modified olefinresins) provide the desired ink receptivity. Specific examples of usefulcopolymers include copolymers of ethylene and vinyl acetate, carbonmonoxide, and methyl acrylate; copolymers of acid and/or acrylatemodified ethylene and vinyl acetate; and terpolymers of ethylene and anytwo polar monomers, for example, vinyl acetate and carbon monoxide.

Other useful ink receptive polymers include urethanes and polyesterssuch as thermoplastic polyurethanes and polyether-ester elastomers.Useful thermoplastic urethane resins include MORTHANE PN343-200,MORTHANE PN 3429-218, MORTHANE PN 03-214, AND MORTHANE L 425 181 fromRohm and Haas, Philadelphia, Pa.; ESTANE 58315 AND ESTANE 58271 andthose sold under the trade designation ELASTOLLAN from BF Goodrich,Cleveland, Ohio; TEXIN DP7-3006 AND TEXIN DP7-3007 from BayerCorporation, Pittsburgh, Pa.; PELLETHANE 2354 AND PELLETHANE 2355 fromThe Dow Chemical Company, Midland Mich.

Useful polyether-ester resins include HYTREL G3548L; HYTREL G4078W; andHYTREL G4778 from E.I. duPont De Nemours, Wilmington, Del. Other usefulcopolyester resins include those available from Eastman Chemical,Kingsport, Tenn. under the trade designation EASTAR.

Commercially available modified olefin resins include: BYNEL 3101, anacid-acrylate modified ethylene vinyl acetate copolymer; ELVALOY 741, aterpolymer of ethylene/vinyl acetate/carbon monoxide; ELVALOY 4924, aterpolymer of ethylene/vinyl acetate/carbon monoxide; ELVALOY 1218AC, acopolymer of ethylene and methyl acrylate; and FUSABOND MG-423D, amodified ethylene/acrylate/carbon monoxide terpolymer (EVACO). All areavailable from E.I. duPont De Nemours, Wilmington Del.

The amount of the three monomers in the terpolymer can range from about50% to about 80% and preferably from about 65% to about 75% weightpercent of ethylene monomer; from about 10% to about 30% and preferablyfrom about 20% to about 24% weight percent of vinyl acetate monomer; andfrom about 4% to about 15% and preferably from about 8% to about 10%carbon monoxide monomer.

The other polymer that can be blended with EVACO polymer typified byELVALOY resin can be any polymer that is effective in use with the EVACOincluding without limitation, ethylene vinyl acetate resins, ethylene(meth)acrylic acid copolymer resins, polyethylene resins, polypropyleneresins, ionomers, ethylene methyl acrylate resins or acid-modified oracid/acrylate modified ethylene vinyl acetate resins. The acrylateresins are more broadly disclosed as having at least twomonoethylenically unsaturated monomeric units, wherein one monomericunit comprises a substituted alkene where each branch comprises from 0to about 8 carbon atoms and wherein one other monomeric unit comprises a(meth)acrylic acid ester of a nontertiary alkyl alcohol in which thealkyl group contains from 1 to about 12 carbon atoms and can includeheteroatoms in the alkyl chain and in which the alcohol can be linear,branched, or cyclic in nature.

Nonlimiting examples of the first monomeric units include ethylene,propylene, butene, isobutylene, hexene, octene, and the like.Nonlimiting examples of the second monomeric units includemethyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate,2-ethylhexyl acrylate, ethoxyethyl acrylate, hexyl acrylate, and thelike. Of these polymers, ethylene methyl acrylates (EMAc) and ethyleneethyl acrylates (EEAc) are preferred because of their commercialavailability. The polymer can be a random or block copolymer

Preferably, the number of carbon atoms ranges from 2 to about 4 for thefirst monomeric unit and from 4 to about 8 for the second monomeric unitalthough the number of carbon atoms can be the same or different, and amixture of different carbon length monomers can be used.

The quantity of polymers of the present invention in the image receptivelayer is preferably maximized within the limits of performancerequirements of the image receptor medium. Routine efforts could beneeded to optimize this quantity. The optimum quantity will depend uponthe desired application and the targeted cost for the image receptormedium.

Where the ink-receptive polymer component comprises a blend of two ormore ink receptive polymers (such as a blend of a (meth)acrylatecopolymer and an ethylene/vinyl acetate/carbon monoxide terpolymer), theblend weight ratio of can be from 100:0 to about 5:95 and preferablyfrom about 85:15 to about 15:85 and most preferably about 80:20 to20:80, the desired ratio depending significantly on the chemicalproperties of the other resin blended with the ethylene/vinylacetate/carbon monoxide terpolymer and can be determined without undueexperimentation by one skilled in the art.

The ink absorptive polymer component is generally present in the imagereceptive layer in amounts of from about 2 to 40 weight percent,preferably 8 to 20 weight percent, relative to the weight of theimmiscible polymer blend. Further, the ink absorptive polymer is presentin amounts such that the absorptive polymer forms a discreet,discontinuous phase in a continuous matrix, and on the surface, of thesemicrystalline polymer.

In a preferred embodiment, the ink absorptive polymer component maycomprise a miscible or immiscible mixture of two or more ink absorptivepolymers, each of which may be chosen to be immiscible with thesemicrystalline polymer component. In a particularly preferredembodiment such a mixture comprises a (meth)acylate copolymer and anethylene/vinyl acetate/carbon monoxide terpolymer, as previouslydescribed.

The semicrystalline polymer component and the ink absorptive polymercomponent are chosen so as to form an immiscible mixture. As usedherein, “immiscibility” refers to polymer blends with limited solubilityand non-zero interfacial tension, i.e. a blend whose free energy ofmixing is greater than zero:ΔG_(m)≅ΔH_(m)>0

Miscibility of polymers is determined by both thermodynamic and kineticconsiderations. Common miscibility predictors for non-polar polymers aredifferences in solubility parameters or Flory-Huggins interactionparameters. For polymers with non-specific interactions, such aspolyolefins, the Flory-Huggins interaction parameter can be calculatedby multiplying the square of the solubility parameter difference withthe factor (V/RT), where V is the molar volume of the amorphous phase ofthe repeated unit, R is the gas constant, and T is the absolutetemperature. As a result, Flory-Huggins interaction parameter betweentwo non-polar polymers is always a positive number.

With the immiscible polymer blend used in the invention, the relativeamounts of the semicrystalline polymer component and ink absorptivepolymer component may be chosen so the first semicrystalline polymercomponent forms a continuous phase and the second absorptive polymercomponent forms a discontinuous phase. The relative amounts of eachpolymer can vary widely, but generally the amount of the ink absorptivecomponent in the composition is from 2% by weight to 40% by weight, morepreferably from 8% by weight to 20% by weight with respect to theimmiscible polymer blend.

In such constructions, the amount of ink absorptive component willaffect final film properties. In general, as the amount of the inkabsorptive component increases, the amount of voiding in the finalbiaxially oriented film also increases. As a result, properties that areaffected by the amount of voiding in the film, such as mechanicalproperties, density, light transmission, etc., will depend upon theamount of added ink absorptive component. When the amount of inkabsorptive polymer in the blend is increased, a composition range willbe reached at which the ink absorptive polymer can no longer be easilyidentified as the dispersed or discrete phase. Further increase in theamount of ink absorptive polymer in the blend will result in a phaseinversion wherein the ink absorptive polymer becomes the continuousphase.

Additionally, the selected ink absorptive component must be immisciblewith the semicrystalline polymer component selected. In this context,immiscibility means that the discrete phase does not dissolve into thecontinuous semicrystalline polymer phase in a substantial fashion, i.e.,the discrete phase must form separate, identifiable domains within thematrix provided by the continuous phase. It has been found that in theabsence of ink receptive polymer component the resulting image receptormedium lacks sufficient porosity at the surface with the result that theink tends to run too much and resolution is impaired. The surfaceporosity allows the applied ink to contact the ink-receptive polymercomponent and absorb the ink solvent.

The inorganic filler may be chosen to have an average particle size offrom about 0.1 to 25 microns and may be any shape including amorphousshapes, spindles, plates, diamonds, cubes, needles, fibers and spheres.Useful inorganic solids useful as inorganic filler components includesolid or hollow glass, ceramic or metal particles, microspheres orbeads; zeolite particles; inorganic compounds including, but not limitedto metal oxides such as titanium dioxide, alumina and silicon dioxide;metal, alkali- or alkaline earth carbonates, silicates, metasilicates orsulfates; kaolin, talc, clays, carbon black and the like. Inorganicfiller components are chosen so as to have little surface interaction,due to either chemical nature or physical shapes, when dispersed in thesemicrystalline polymer component. In general the inorganic fillercomponents should not be chemically reactive with the semicrystallinepolymer component, including Lewis acid/base interactions, and haveminimal van der Waals interactions. The role of the filler is to furtherinduce void formation upon stretching by debonding from the polymermatrix.

The inorganic fillers such as crystalline and amorphous silica, clayparticles, aluminum silicate, titanium dioxide and calcium carbonate,and the like impart one or more of desirable properties such as improvedsolvent absorption, improved dot gain and color density, opacity andimproved abrasion resistance. Preferably such fillers are coated toreduce agglomeration and improve dispersability. The amount of suchfillers in the image receptive layers of the invention typically rangefrom about 20% to about 50% by weight, relative to the total weight ofimage receptive layer (i.e. semicrystalline polymer component, inkabsorptive polymer component and filler). Preferably, the amount offillers is at least about 30%, most preferably 40% by weight.

To enhance durability of the image receptive layer, especially inoutdoor environments exposed to sunlight, a variety of commerciallyavailable stabilizing chemicals can be added optionally to the primercompositions. These stabilizers can be grouped into the followingcategories: heat stabilizers, UV light stabilizers, and free-radicalscavengers.

Heat stabilizers are commonly used to protect the resulting imagegraphic against the effects of heat and are commercially available fromWitco Corp., Greenwich, Conn. under the trade designation Mark V 1923and Ferro Corp., Polymer Additives Div., Walton Hills, Ohio under thetrade designations Synpron 1163, Ferro 1237 and Ferro 1720. Such heatstabilizers can be present in amounts ranging from about 0.02 to about0.15 weight percent.

Ultraviolet light stabilizers can be present in amounts ranging fromabout 0.1 to about 5 weight percent of the total primer or ink.Benzophenone type UV-absorbers are commercially available from BASFCorp., Parsippany, N.J. under the trade designation Uvinol 400; CytecIndustries, West Patterson, N.J. under the trade designation CYASORB UV1164 and Ciba Specialty Chemicals, Tarrytown, N.Y., under the tradedesignations TINUVIN 900, TINUVIN 123 and TINUVIN 1130.

Free-radical scavengers can be present in an amount from about 0.05 toabout 0.25 weight percent of the total primer composition. Nonlimitingexamples of free-radical scavengers include hindered amine lightstabilizer (HALS) compounds, hydroxylamines, sterically hinderedphenols, and the like.

HALS compounds are commercially available from Ciba Specialty Chemicalsunder the trade designation TINUVIN 292 and Cytec Industries under thetrade designation CYASORB UV3581.

In general, the image receptive layer is typically substantially free ofcolorant. However, it may also contain colorants to provide a uniformbackground colored film.

In another embodiment of the invention the image receptor medium mayfurther comprise a support layer to reduce the cost and/or enhance thephysical properties of the medium. The support layer is most commonlywhite and opaque for graphic display applications, but could also betransparent, translucent, or colored. Support layer can comprise anypolymer having desirable physical properties for the intendedapplication. Properties of flexibility or stiffness, durability, tearresistance, conformability to non-uniform surfaces, die cuttability,weatherability, solvent resistance (from solvents in inks) heatresistance and elasticity are examples. For example, a graphic markingfilm used in short term outdoor promotional displays typically canwithstand outdoor conditions for a period in the range from about 3months to about one year or more and exhibits tear resistance anddurability for easy application and removal.

The material for the support layer may be a melt-processible polymerwhich may be extruded or coextruded into a substantially two-dimensionalfilm, or may be melt coated, bonded or otherwise affixed to thebiaxially oriented medium. The support layer is preferably resistant tosolvents used in inks. “Resistant to solvents in inks” means that thesupport layer does not absorb significant amounts of the solvents in theink, and does not allow migration of significant amounts of solventthrough the film, if used in combination with an adhesive on theopposite side of the receptor layer. “Significant” means the film doesnot allow enough solvent to pass through the film to negatively impactthe adhesion performance of the underlying adhesive layer. For example,the barrier layer would prevent solvents from plasticizing the adhesivelayer. Typical solvents used in inkjet inks include 2-butoxyethylacetate available from the 3M Company, Saint Paul, Minn. under the tradedesignation 3M SCOTCHCAL™ Thinner CGS-50, 1-methoxy-2-acetoxy-propaneavailable from under the trade designation 3M SCOTCHCAL™ Thinner CGS-10,cyclohexanone, dipropylene glycol methylether acetate, and otheracetates such as those sold under the trade designation EXXATE™available from Exxon Chemical, Houston, Tex. Examples of suitablematerials support layer include polyester, polyolefin, polyamide,polycarbonate, polyurethane, polystyrene, acrylic, or combinationsthereof. Examples of such materials include paper, polypropylene,polyethylene terephthalate, polyethylene coated papers, fabrics,nonwoven materials, scrims, and the like.

The support layer may also contain other components such as pigments,fillers, ultraviolet stabilizing agents, slip agents, antiblock agents,antistatic agents, and processing aids familiar to those skilled in theart. The support layer is commonly white opaque, but may also betransparent, colored opaque, or translucent.

A typical thickness of the support layer is in the range from 0.5 mil(12.7 micrometers) to 12 mils (305 micrometers). However, the thicknessmay be outside this range providing the resulting image receptor mediumis not too thick to feed into the printer or image transfer device ofchoice. A useful thickness is generally determined based on therequirements of the desired application.

If desired, an adhesive layer may be applied to a major surface of theimage receptor medium of the invention. Typically, the adhesive layerwould be applied to a major surface of the support layer of a multilayerarticle comprising the image receptive layer and the support layer. Theadhesive may be applied to the receptor medium by any means known in theart including melt-coating, transfer coating, solvent coating,lamination and extrusion or coextrusion. The adhesive layer may beactivated by pressure, heat, solvent or any combination thereof and maybe of any type based on a poly(α-olefin), a block copolymer, anacrylate, a rubber/resin, or a silicone. The adhesive may be applied atconventional coating weights (e.g., 0.0001 to 0.02 g/cm²) using anyconventional coating means such a slot die or a gravure roll. Thesupport layer may also be treated with a conventional primer coating,and/or activated by flame or corona discharge, and/or by another surfacetreatment to enhance adhesion of the adhesive layer thereto.

Although it is preferable to use a pressure sensitive adhesive, anyadhesive that is particularly suited to the substrate layer and to theselected application can be used. Such adhesives are those known in theart and may include aggressively tacky adhesives, pressure sensitiveadhesives, repositionable or positionable adhesives, hot melt adhesives,and the like.

When a pressure sensitive adhesive (psa) layer is used, pressuresensitive adhesives useful in the present invention can be self-tacky orrequire the addition of a tackifier. Such materials include, but are notlimited to, tackified natural rubbers, tackified synthetic rubbers,tackified styrene block copolymers, self-tacky or tackified acrylate ormethacrylate copolymers, self-tacky or tackified poly-α-olefins, andtackified silicones. Examples of suitable pressure sensitive adhesivesare described in U.S. Pat. No. Re 24,906 (Ulrich), U.S. Pat. No.4,833,179 (Young et al.), U.S. Pat. No. 5,209,971 (Babu et al.), U.S.Pat. No. 2,736,721 (Dexter), U.S. Pat. No. 5,461,134 (Leir et al.), U.S.Pat. No. 4,391,687 (Vesley), U.S. Pat. No. 4,330590 (Vesley) and U.S.Pat. No. 5,112,882 (Babu), the entire disclosure of which isincorporated herein by reference. Others are described in theEncyclopedia of Polymer Science and Engineering, vol. 13,Wiley-Interscience Publishers, New York, 1988, the Encyclopedia ofPolymer Science and Technology, vol. 1, Interscience Publishers, NewYork, 1964 and Handbook of Pressure-Sensitive Adhesives, D. Satas,Editor, 2^(nd) Edition, Von Nostrand Reinhold, New York, 1989.

A prime layer may be used to increase the bond strength between thesupport layer and an adhesive layer if the bond strength is notsufficiently high without the prime layer. The presence of an adhesivelayer makes the image receptor medium useful as an adhesive backedgraphic marking film.

The image receptor media of the invention may also have an optional tielayer (not shown) between image receptive layer and the support layer. Atie layer is used to improve adhesion between the image receptive layerand the support layer. Useful tie layers include extrudable polymerssuch as ethylene vinyl acetate polymers, and modified ethylene vinylacetate polymers (modified with acid, acrylate, maleic anhydride,individually or in combinations). The tie layer may consist of thesematerials by themselves or as blends of these polymers with thesemicrystalline polymer component. Use of tie layer polymers is wellknown in the art and varies depending on the composition of the twolayers to be bonded. Tie layers for extrusion coating could include thesame types of materials listed above and other materials such aspolyethyleneimine that are commonly used to enhance the adhesion ofextrusion coated layers. Tie layers can be applied to the support layeror ink absorptive layer by coextrusion, extrusion coating, laminating,or solvent coating processes.

The inks particularly useful in combination with the coextrudedconstruction of the invention include the SCOTCHCAL™ 3700 series andSCOTCHCAL™ 4000 series solvent-based piezo inkjet inks, available fromthe 3MCompany, St. Paul, Minn., the ULTRAVU™ series solvent-based piezoinkjet inks, available from VUTEK, Meredith, N.H., and the ARIZONA™1100-3 solvent-based inks, available from RasterGraphics of the GretagImaging Group, San Jose, Calif. Such inks typically consist of acolorant, dye, or pigment, a dispersant if pigment is used, a binder,and a blend of solvents. Additional optional components includestabilizers, flow agents, viscosity modifiers, and others. A detaileddescription of a typical solvent-based inkjet ink formulation can befound in U.S. Pat. No. 6,113,679.

Generally, the image receptor layer is prepared from a melt-blendobtained by feeding a mixture of the semicrystalline polymer, theink-absorptive polymer and the inorganic filler into a hopper of anextruder. This mixture is conveyed through the extruder that is heated,preferably with individually controlled temperature zones heated atincreasing temperatures toward the extruder exit to a slot die that hasa slit gap of 25 to 1,000 micrometers. Preferably, the semicrystallinepolymer is fed into a hopper of the extruder and the additionalcomponents are fed by a suitable device into the extruder via a port inthe extruder wall intermediate to the hopper and the extruder exit. Itis also preferable to utilize a suitable mixing device such as a staticmixer between the extruder exit and the slot die. In passing through theextruder, and, where used, the static mixer, the mixture of polymer andadditional components are heated to a temperature at or above the glasstransition temperature of the semicrystalline polymer (but below thethermal degradation temperature of the polymer) and mixed to form amelt-blend solution that is extruded through a slot die as a film layerinto a liquid quench bath maintained at a suitable temperature below theglass transition temperature of the semicrystalline polymer using asuitable coolant, e.g., water. The cooled film may then be fed from thequench bath to a machine-direction orienting device, a transversedirection-orienting device (or a simultaneous orienting device) and thento a take-up roller.

Generally, the film is cast onto a temporary carrier web, but the imagereceptive layer may also be coextruded with, or melt-cast onto, asupport layer. Typically, the image receptive layer is at least 0.5 mils(12.7 micrometers) thick, and preferably between 0.7 mils (17.8micrometers) and 4 mils (102 micrometers).

The image receptive layer is then oriented to impart voids to thereceptor. Generally, it is preferred to orient a film consisting of onlya single layer of the image receptive layer, although multilayerarticles such an image receptive layer and a support layer may beoriented. Upon orientation, voids are imparted to the image receptivelayer, which assumes a porous, three-dimensional cellular structurehaving a network of interconnected adjacent cells to allow passage offluid from one major surface, through the thickness of the imagereceptor layer to the opposite major surface. As the image receptivelayer is stretched, the components (the semicrystalline polymercomponent, the ink absorptive polymer component and the inorganicfiller) separate due to the immiscibility of the components and pooradhesion between the phases. As the image receptive layer comprises acontinuous phase and a discontinuous phase, the discontinuous phase(s)serves to initiate voids that remain as substantially discrete,discontinuous irregularly shaped phases in the cellular matrix of thecontinuous phase. The porous, voided structure of the ink-receptivelayer allows the ink to contact the ink-receptive polymer so that thesolvent may be absorbed. The lack of a porous, voided structure willresult in poor image resolution as the ink bleeds on the surface of thelayer, rather than drying by absorption of the ink solvent by the inkabsorptive polymer component. It will be understood that a support layeraffixed to the image receptive layer may block the porosity of one majorsurface, but not the porous matrix of the image receptor layer or othermajor surface thereof.

The conditions for orientation are chosen such that the integrity of theimage receptive layer is maintained. Thus when stretching in the machineand/or transverse directions, the temperature is chosen such thatsubstantial tearing or fragmentation of the continuous phase is avoidedand image receptive layer integrity is maintained. The image receptivelayer is particularly vulnerable to tearing or even catastrophic failureif the temperature is too low, or the orientation ratio(s) is/areexcessively high. Preferably, the orientation temperature is above theglass transition temperature, but below the melt temperature, of thecontinuous phase. Such temperature conditions permit maximum orientationin the machine (X) and transverse (Y) directions without loss of filmintegrity, maximize voiding imparted to the image receptive layer.

Voids arise due to both the poor stress transfer between the polymericphases of the immiscible blend and debonding from the inorganicparticulates. It is believed that low molecular attractive forcesbetween the blend components are responsible for immiscible phasebehavior; low interfacial tension results in void formation when theimage receptive layers are stressed by orientation or stretching.Typical voids have major dimensions X and Y, proportional to the degreeof orientation in the machine and transverse direction respectively. Aminor dimension Z, normal to the plane of the image receptive layer, mayremain substantially the same as the cross-sectional dimension of thediscrete phase (ink absorptive polymer) prior to orientation if orientedat a temperature below the T_(g) of the ink absorptive polymer, or maybe substantially reduced if oriented at a temperature above the T_(g) ofthe ink absorptive polymer.

It is preferred that the biaxial orientation is such that the resultingvoids at the surface have an average diameter (in the X and Ydirections) less than or equal to the average size of the inkjetdroplets applied thereto. The inkjet droplets have an average size ofabout 70 micrometers for currently available inkjet printers. Thus thevoids may have an average major diameter of less than or equal to 70micrometers and it is preferred that the voids have an average majordiameter of about 10 to 70 micrometers.

Voids of the open cellular structure are relatively oblate ellipsoidalin shape, irregular in size, and have semi-continuous boundaries asresult of adjacent voids having apertures therebetween to impart aporous morphology to the ink receptive layer. Voids are generallycoplanar with the film, with major axes in the machine (X) andtransverse (Y) directions (directions of orientation). The size of thevoids is variable and proportional to the size of the discrete phase anddegree of orientation. Image receptive layers having relatively largedomains of discrete phase and/or relatively high degrees of orientationwill produce relatively large voids. Image receptive layers having ahigh proportion of discrete phases will generally produce imagereceptive layers having a relatively high void content on orientation.Void size, distribution and amount in the image receptive layer matrixmay be determined by techniques such as small angle x-ray scattering(SAXS), confocal microscopy, scanning electron microscopy (SEM) ordensity measurement.

Generally, greater void content enhances the quality of the print orimage imparted to the image receptor medium. It is believed that theopen cellular structure provides a large surface area to enhance the inkflow on the surface and the absorption of the ink solvent by the inkabsorptive polymer component, which is advantageously exposed to the inkby the voiding and open cellular structure. Preferably, the imagereceptive layer should have a void content in excess of 30%, preferablyin excess of 50%, more preferably in excess of 60% as measured bydensity; i.e., the ratio of the density of the voided image receptivelayer with that of the starting image receptive layer.

In the orienting step, the image receptive layer is stretched in themachine direction (X axis) and simultaneously or sequentially stretchedin the transverse direction to impart a biaxial orientation to the imagereceptive layer. The stretching conditions are chosen to impart voids(in excess of 30% as measured by the change in density) and therequisite open porous structure to the film. The occurrence of asignificant amount of voids will impart a translucent, opalescent orsilvery appearance to the surface of the image receptive layer due tolight scattering from the defects. The presence of voids may be verifiedby small-angle x-ray or density measurement, or by microscopy.

Stretching in mutually perpendicular directions at a temperature abovethe glass transition temperature of the semicrystalline polymercontinuous phase may biaxially orient the image receptive layer.Generally, the film is stretched in one direction first and then in asecond direction perpendicular to the first. However, stretching may beeffected in both directions simultaneously if desired. In a typicalprocess, the film is stretched first in the direction of extrusion overa set of rotating rollers or between two pairs of nip rollers and isthen stretched in the direction transverse thereto by means of a tenterapparatus. Films may be stretched in each direction up to 2 to 10 timestheir original dimension in the direction of stretching. The imagereceptive layer may be biaxially stretched 5× to 100× total draw ratio,which is defined herein as the ratio of the final area to the initialarea of the image receptor medium.

When sequentially oriented, the temperature of the first orientation (orstretching) affects image receptive layer. Generally, the firstorientation step is in the machine direction. Orientation temperaturecontrol may be achieved by controlling the temperature of heated rollsor by controlling the addition of radiant energy, e.g., by infraredlamps, as is known in the art. A combination of temperature controlmethods may be utilized.

Too low an orientation temperature may result in a film with an unevenappearance. Increasing the first orientation temperature may reduce theuneven stretching, giving the stretched film a more uniform appearance.The first orientation temperature also affects the amount of voidingthat occurs during orientation. In the temperature range in whichvoiding occurs, the lower the orientation temperature, generally thegreater the amount of voiding that occurs during orientation. As thefirst orientation temperature is raised, the degree of voiding decreasesto the point of elimination. Electron micrographs of samples show thatat temperatures at which no voiding occurs, the discrete phases domainsoften deform during stretching. If sequential, the temperature of suchsecond orientation is generally similar to or higher than thetemperature of the first orientation.

Using polypropylene, for example, as the semicrystalline polymercomponent, the first orientation, in the machine direction, may beconducted at temperature from about 60–160° C., and then in thetransverse direction at temperature from about 130–160° C. If orientedsimultaneously in the machine and transverse direction, temperaturesfrom about 130–160° C. are found to be useful.

After the film has been stretched it may be further processed. Forexample, the film may be annealed or heat-set by subjecting the film toa temperature sufficient to further crystallize the semicrystallinepolymer component while restraining the film against retraction in bothdirections of stretching. Further, the image receptive layer may belaminated, bonded or otherwise affixed to a support layer. If atwo-layer article comprising the image receptive layer and a supportlayer is provided, (by coextrusion or prior lamination for example) thesupport layer should be chosen so that it may be oriented as well. Inembodiments where the image receptive layer is coextruded with a supportlayer, it is preferable to orient the composite article as it exits thedie. Thus a composite article comprising an image receptive layer, asupport layer, and optionally a tie layer, may be fed from the extruderto the orienting apparatus.

The image receptive layer, alone or with a support layer, may also beprovided with an adhesive layer after orientation as well.

The final thickness of the image receptive layer will be determined inpart by the casting thickness, the degree of orientation, and anyadditional processing such as calendering. For most uses, the finalthickness of the image receptive layer will be 1 to 20 mils (0.025 to0.5 mm), preferably 3 to 10 mils (0.075 to 0.25 mm). The article of theinvention will generally exhibit a color density measurement of at leastabout 1.1, preferably at least about 1.2 and most preferably at leastabout 1.3 as measured by densitometry. Additionally the articles mayexhibit a two-color resolution of at least 0.5 mm as measured by the“two-color line width resolution test” described herein. The colordensity is generally a function of the ink-absorptive polymer, asselected by the Inclined Ink Trail Test for a particular ink (andcorresponding ink solvent) and printing technique used. The resolutionis generally a function of the average surface pore size, which shouldbe equal to or less than the average ink droplet applied thereto.Further, the average surface pore size is a function of the degree oforientation, amount of inorganic filler, and the amount of ink-receptivepolymer used. An iterative process to optimize the resolution for agiven ink and printing technique may adjust each of these.

The biaxially oriented articles may be a finished product (withprinting) or an intermediate and are useful for a variety of articlesincluding signage and graphics films. Signage includes variousretroreflective sheeting products for traffic control as well asnon-retroreflective signage such as backlit signs.

The article is suitable for use as roll-up signs, flags, banners andother articles including other traffic warning items such as roll-upsheeting, cone wrap sheeting, post wrap sheeting, barrel wrap sheeting,license plate sheeting, barricade sheeting and sign sheeting; vehiclemarkings and segmented vehicle markings; pavement marking tapes andsheeting; as well as graphics films. Graphic films include a variety ofadvertising, promotional, and corporate identity imaged films. The filmstypically comprise a pressure sensitive adhesive on the non-viewingsurface in order that the films can be adhered to a target surface suchas an automobile, truck, airplane, billboard, building, awning, window,floor, etc.

Objects and advantages of the invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in the examples, as well as other conditions and details, shouldnot be construed to unduly limit the invention. All parts, percentagesand ratios herein are by weight unless otherwise specified.

EXAMPLES

Printing Method

Unless specified otherwise, a Xaar Jet XJ128-100 piezoelectric inkjetprinthead (available from Xaar Ltd., Cambridge, England) on an x-ytranslational stage at 317 by 295 dots per inch resolution was employedto print test patterns. The test patterns consisted of filled squaresand lines printed at 100%–400% ink lay down. These patterns were used toevaluate image quality. The inks that were used were SCOTCHCAL 3700series inks (available from 3M, St. Paul, Minn.), specifically 3791magenta, 3792 yellow, 3795 black and 3796 cyan.

Test Methods

Test Method 1: Draw Ratio Measurements

The machine direction (MD) and transverse direction (TD) draw ratios ofbiaxially oriented films were determined by inscribing equally spacedlines perpendicular to both of the stretching directions prior tostretching and by calculating the corresponding ratio of the final linespacing (after stretching) to the initial spacing.

Test Method 2: Density Measurement and Void Content Determination

Densities of cast sheets and oriented films were measured at 21° C. indeionized water according to the method of ASTM D792-00. Each filmsample was weighed on a Mettler AG285 high precision balance(manufactured by Mettler-Toledo, Inc., Columbus, Ohio) and then placedunderwater. The buoyant force of the water on the sample was measuredusing the density determination apparatus (Kit #238490, manufactured byMettler-Toledo, Inc., Columbus, Ohio). The volume of water displaced bythe sample was thereby determined and, in combination with the sampleweight, used to calculate the sample density. The void content was thencalculated as follows:Calculated % Void Content={1−(final density/initial density)}×100where the initial density is the density of the cast film beforeorientation, and the final density is the density of the oriented film.Test Method 3: Image Quality Evaluation

Image quality was evaluated using the printing test patterns describedabove by observing characteristics such as inter-color bleed, coloruniformity, edge sharpness, and overall appearance of the test pattern.To quantitatively compare the ability of a film to control inter-colorbleed and maintain high resolution, arrays of alternating parallel linesof two different colors (red and black) were printed immediatelyadjacent to one and other. The red lines were printed at 200% inkcoverage, and the black lines were printed at 400% ink coverage, butboth red and black lines were printed at the same width. A number ofthese arrays of alternating black and red lines were printed on asubstrate with each array having a different characteristic line widthranging from 0.085 mm to 0.68 mm. The smallest line width that was stilleasily resolved on a given substrate as its “two-color line widthresolution” (TLWR). Thus, a substrate having a smaller TLWR will havesuperior resolution and less inter-color bleed than a substrate having alarger TLWR.

Solid block color density (CD) was measured using a Gretag SPM-55densitometer, available from Gretag-MacBeth AG, Regensdorf, Switzerland.Specifically, CD of a solid black square printed at 100% ink lay-downwas measured at a wavelength of 410 nm and an observer angle of 2°. Nobackground subtraction was used, and the reported values were theaverage of three measurements. An increase in CD correlated to anincrease or improvement in solid ink fill.

The dryness of ink immediately after printing was noted by lightlytouching a piece of paper to the test pattern and observing if any inktransferred from the substrate to the paper.

Test Method 4: Inclined Ink Trail Test

The Inclined Ink Trail Test was designed to screen potentialink-receptive polymer components that are useful for blending withpolypropylene in order to make ink receptive films. Vinyl films wereused as a standard since they are known to provide high image qualitywhen printed with the testing ink. Three vinyl films were used asstandards: CONTROLTAC PLUS Vinyl Film 180-10, SCOTCHCAL 3555 Vinyl Film(both available from 3M, St. Paul, Minn.), and MPI 1005 cast vinyl film(available from Avery Dennison Graphics Division, Hazerswoude, TheNetherlands). The standard films were wiped with isopropanol prior totesting. Potential ink-receptive polymer components were cast as flatsheets either by solvent-casting or extrusion. These flat sheet filmswere adhered to a 45-degree inclined plane and were conditioned at roomtemperature (21° C.) prior to testing. The inclined plane was 40 cm inlength. The ink receptivity of the films was evaluated by depositing a10 μl droplet of inkjet ink (black, SCOTCHCAL 3795, 3M) using a 25 μlsyringe at the top of the incline. The ink was allowed to run down theincline until it stopped due to evaporation or absorption into the film.The distance that the ink traveled (three trials each) was recorded andcompared to ink traveling on standard materials. In addition an InkTrail Number (IT#) was recorded as the ratio of the distance the inktraveled compared to CONTOLTAC PLUS Vinyl film 180-10. Additives whichproduced films with an IT# closest to one (closest in behavior in theInclined Ink Trail Test to vinyl film) were used to make further blendsand are described in the examples. The potential polymer additives thatwere screened are shown in Table 1.

TABLE 1 Polymers Evaluated in Inclined Ink Trail Test MaterialComposition Vendor FINA 3376 Polypropylene Atofina, Inc., Houston, TXCP-80 Clear Poly(methyl Ineos Acrylics, Cordova TN methacrylate) ELVALOY741 Ethylene/vinylacetate/ Dupont, Wilmington, DE carbon monoxide ELVAX240 Ethylene/vinyl acetate Dupont, Wilmington DE ENGAGE 8200Ethylene/1-octene Dow Dupont, Wilmington, DE KRATON Stryene/isopreneblock Kraton Polymers, Houston D-1107 copolymer TX LURAN 358NStyrene/acrylonitrile BASF, Mount Olive, NJ PARALOID B-67 Poly(isobutylRohm & Haas, methacrylate) Philadelphia, PA

All of the polymer additives except the PARALOID B-67 were prepared asfilms for Inclined Ink Trail testing by extrusion using the followingprocess: The resins were extruded using a PLASTI-CORDER Laboratory batchmixer (type DR-2051, manufactured by C. W. Brabender Instruments, Inc.,South Hackensack, N.J.) equipped with a ¾′ (19 mm) single screw extruderand a 6′ (15.2 cm) wide ribbon die (manufactured by Extrusion Dies,Inc., Chippewa Falls, Wis.) having a gap of 0.30 mm operating at 200° C.and 80 rpm. The molten polymer films were cast onto a 0.05 mm polyestercarrier film (SCOTCHPAK 970197, available from 3M, St. Paul, Minn.) andthen passed through a 3 roll chilled stack and wound up. The films were0.10–0.13 mm in thickness. The PARALOID B-67 was cast from solvent. 40%by weight of resin was dissolved in 2-butoxyethyl acetate (SCOTCHCALThinner CCS-50 available from 3M, St. Paul, Minn.). This solution wascoated using a notched bar coater set with a 0.025 mm gap onto the samepolyester carrier film. The film was dried at 65° C. for 1 hour to driveoff the solvent.

In Table 2 the results of the Inclined Ink Trail test are shown forfilms of the potential polymer additives in Table 1 as well as the threestandard vinyl films described above. The results in Table 2 indicatethat there is only a minor difference between the ink trail lengthobtained on the three different vinyl films, although these films havedifferent thicknesses and are from different manufacturers. In all threecases, the average ink trail length was measured to be approximately 8.5cm±0.4 cm. This observation suggests that this test is a good measure ofthe net interaction of an ink with a given type of resin. Forpolypropylene, the ink trail was longer than the length of the inclinedplane, demonstrating the very low affinity of the ink for polypropylene.For the potential print additives, the trail lengths ranged from 6.25 to17 cm, indicating that there is a wide variation in the affinity of theink for the various resins.

TABLE 2 Results for inclined ink running test Material Ink Trail Length(cm) IT# 3M Controltac Plus Vinyl Film 180–10 8.8 1.00 3M Scotchcal 3555Vinyl Film 8.9 1.01 Avery MPI ™ 1005 cast Vinyl Film 8.2 0.93FINA3376 >40 large CP-80 Clear 16.6 1.89 Elvaloy 741 7.6 0.86 Elvax 2409.8 1.11 Engage 8200 17 1.93 Kraton D-1107 6.3 0.72 Luran 358N 7.5 0.85Paraloid B-67 8.6 0.98

Comparative Example C1

This comparative example is a demonstration of solvent-basedpiezoelectric inkjet printing on a commercially available vinyl graphicsfilm (CONTROLTAC PLUS Graphic Film 180-10, available from 3M Company,St. Paul, Minn.). The vinyl film was cleaned with isopropyl alcohol toremove any contaminants and then printed upon using the Xaarpiezoelectric inkjet printer as described above.

Image Quality: The ink coverage on the film surface was uniform with nosignificant mottling. Evaluation of the test pattern indicated that theTLWR was 0.50 mm. The CD was 1.92. Thus, the image quality of thissubstrate was regarded as being very good. Its primary deficiency isthat the ink was still very wet immediately after printing.

Comparative Example C2

This comparative example is a demonstration of solvent-basedpiezoelectric inkjet printing on a microporous film.

Sample Preparation: A microporous film was prepared via the method ofthermally induced phase separation as described in U.S. Pat. No.5,120,594. The film was 5.5 mils thick and had 40% voids and pore sizesin the range of 0.5–0.8 um as indicated by the scanning electronmicroscopy (SEM) image.

Image Quality: The microporous film sample was printed upon using theXaar piezoelectric inkjet printer as described above. The ink coverageon the film surface was uniform with no significant mottling. Evaluationof the test pattern indicated that the TLWR was 0.42 mm. The CD was0.95. Although this substrate yields superior resolution than C1, its CDis extremely low. Both of these results are due to the high degree ofcapillarity associated with the microporous structure. The microporesprevent inter-color bleeding and provide high resolution, but they alsodraw the ink away from the surface and cause the image color density tofade. It was also observed that the ink was completely dry immediatelyafter printing, a result that is also due to the micropores drawing theink rapidly away from the surface.

Comparative Example C3

This comparative example is a demonstration of solvent-basedpiezoelectric inkjet printing on a multi-layer biaxially oriented filmcomprised of a voided core layer containing polypropylene and aninorganic filler, and thin non-void surface layers.

Sample Preparation: A multi-layer sheet was prepared consisting of acore layer containing 60 weight % polypropylene homopolymer (FINA 3376available from Atofina, Inc., Houston, Tex.) and 40 weight % calciummetasilicate (wollastonite Micronite 800H available from Fibertec Inc.,Bridgewater, Mass.) with thin surface layers of polypropylenehomopolymer. The core layer was compounded in a 60 mm twin screwextruder (available from Berstorff GmbH, Hannover, Germany) and thesurface layers were supplied via a 38 mm single screw extruder(available from Davis-Standard, Pawcatuck, Conn.). The two extruders fedthe materials into a feedblock and die (supplied by Cloeren Inc.,Orange, Tex.), and the sheet was cast onto a chrome wheel half-submersedin a water bath. The extruders and feedblock/die were both operated at250° C., and the cast roll and water bath were operated at 20° C. Thecast sheet produced was 1.5 mm thick, with each surface layerapproximately 0.03 mm thick. The cast sheet had a density of 1.22 g/cm³.

From the cast sheet, 85 mm×85 mm square specimens were cut out andbiaxially oriented in a Karo IV Laboratory Stretcher (manufactured byBrückner Maschinenbau GmbH, Siegsdorf, Germany) at 160° C. Asimultaneous balanced stretch at 4.2 m/min in both the MD and the TD wasemployed, resulting in a final biaxial draw ratio of 3.5×3.5 (MD×TD) asdetermined by Test Method 1. The resulting oriented film had a thicknessof approximately 0.1 mm and a density of 0.82 g/cm³, indicating a voidcontent of 33% as per Test Method 2.

Image Quality: The voided film sample was printed upon using the Xaarpiezoelectric inkjet printer as described above. The ink coverage on thefilm surface was very non-uniform with significant mottling andcoalescing of the ink. Because of the high degree of inter-colorbleeding, the test pattern was not resolvable, and it was not possibleto measure a TLWR. Although the ink coverage was non-uniform, it waspossible to measure a solid block CD in certain regions of 1.7. It wasalso observed that the ink was very wet immediately after printing.Thus, although this substrate is highly voided internally, it is notporous enough to physically draw the ink away from the surface, as isthe case for example C2. Because polypropylene has a very low affinityfor the ink (cf. Table 2) ink does not dissolve into the substrate.Thus, the ink remains on the surface, and at high ink coverage, it tendsto bleed because there is no interaction with the surface to keep itfrom flowing. The final result is a very poor image quality.

Comparative Example C4

This comparative example is a demonstration of solvent-basedpiezoelectric inkjet printing on a biaxially oriented voided filmcomprised of polypropylene and an inorganic filler.

Sample Preparation: A 75 g batch of 64 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with36 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.) was compounded at 200°C. in a Plasti-Corder Laboratory batch mixer (type DR-2051, manufacturedby C. W. Brabender Instruments, Inc., South Hackensack, N.J.) untilmelted (roughly three to five minutes at 50 to 100 RPM). The resultingmixture was then pressed into a sheet between metal platens, using a0.09 cm spacer shim, in a hot press (model G-30H-1S-LP manufactured byWabash MPI, Wabash, Ind.) at 200° C. under a load of 454 kg for 3 min,followed by pressing under a load of 18,160 kg for an additional 30seconds, and finally quenched between cold clamps cooled with runningtap water for 3 minutes. The density of the resulting pressed sheet was1.18 g/cm³ and the thickness was approximately 1 mm.

From the pressed sheet, 85 mm×85 mm square specimens were cut out andbiaxially oriented in a Karo IV Laboratory Stretcher (manufactured byBrückner Maschinenbau GmbH, Siegsdorf, Germany) at 150° C. Asimultaneous balanced stretch at 4.2 m/min in both the MD and the TD wasemployed, resulting in a final biaxial draw ratio of 6×6 (MD×TD) asdetermined by Test Method 1. The resulting oriented film had a thicknessof approximately 0.05 mm and a density of 0.50 g/cm³, indicating a voidcontent of 58% as per Test Method 2. SEM images of the surface andcross-section of the voided film indicate that although the film isindeed highly voided, the surface is substantially non-porous.

Image Quality: The voided film sample was printed upon using the Xaarpiezoelectric inkjet printer as described above. As with example C3, theink coverage on the film surface was very non-uniform with significantmottling and coalescing of the ink. Indeed the test pattern was notresolvable, making it impossible to measure a TLWR. It was possible tomeasure a solid block CD in certain regions of 1.57. It was alsoobserved that the ink was very wet immediately after printing. As withexample C3, this poor image quality is a result of the low porosity andlow affinity of the ink for the polypropylene surface. SEM reveals thesurface has only a meager number of pores even though it has beenstretched significantly and is over 50% voids. Thus, it is not enough tosimply orient a particulate filled-polypropylene film to generate aporous substrate suitable for inkjet printing.

Example 1

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with inorganic filler, and a terpolymer of ethylene/vinylacetate/carbon monoxide.

Sample Preparation: A 75 g batch of 64 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.) and 5 weight % of aterpolymer of ethylene/vinyl acetate/carbon monoxide (ELVALOY 741available from DuPont Packaging and Industrial Polymers, Wilmington,Del.) was compounded in the same manner as described in example C4. Thedensity of the resulting pressed sheet was 1.27 g/cm³ and the thicknesswas approximately 1 mm.

From the pressed sheet, 85 mm×85 mm square specimens were cut out andbiaxially oriented in a Karo IV Laboratory Stretcher at 150° C. asdescribed in example C3, resulting in a final biaxial draw ratio of3.5×3.5 (MD×TD) as determined by Test Method 1. The resulting orientedfilm had a thickness of approximately 0.2 mm and a density of 0.44g/cm³, indicating a void content of 65% as per Test Method 2. FIGS. 1and 2 show SEM images of the surface and cross-section of the orientedfilm, indicating that the film is highly voided with a surface that isporous.

Image Quality: The porous film sample was printed upon using the Xaarpiezoelectric inkjet printer as described above. In contrast to examplesC3 and C4, the ink coverage on the film surface was very uniform with nosignificant mottling. Evaluation of the test pattern indicated that theTLWR was 0.42 mm, equivalent to that of the microporous film, exampleC2. The CD was 1.24, which is greater than example C2, but less than theCDs of C3 and C4, indicating that some of the ink was drawn into thepores away from the surface. This transfer of ink away from the surfacedecreased the CD but resulted in an increase in resolution and controlof inter-color bleeding as indicated by the lower value of TLWR. It wasalso observed that the ink was only slightly wet immediately afterprinting. As shown in FIG. 1, the surface has a significant number ofpores that are generally less than 100 μm in diameter. It appears thatadding the second resin significantly improved the image quality overthe other oriented polypropylene films (Examples C2, C3, and C4). Thisis because the presence of the second resin resulted in an increase inthe number of surface pores, allowing the control of inter-colorbleeding (in contrast to C3 and C4) and also because it's higheraffinity for the ink (see Table 2) caused the CD to remain relativelyhigh (in contrast to C2). Finally, the porosity of the film served toincrease the rate of ink drying of the film over that of C1, C3, and C4.

Example 2

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with inorganic filler, and a terpolymer of ethylene/vinylacetate/carbon monoxide.

Sample Preparation: A sample was compounded, pressed, and stretched inthe same manner as Example 1 except that the final biaxial stretch was5.5×5.5 (MD×TD) as determined by Test Method 1. The resulting orientedfilm had a thickness of approximately 0.065 mm and a density of 0.33g/cm³, indicating a void content of 74% as per Test Method 2. SEM imagesof the surface and cross-section of the oriented film indicate that thefilm is highly voided with a surface that is porous. In comparison toExample 1, the interior of the film is composed of thinner layers ofpolymer that are more widely spaced, resulting in the higher voidcontent. These differences are due to the larger draw imposed on thefilm during orientation.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. Similar to Example 1,the ink coverage on the film surface was uniform with no significantmottling. Evaluation of the test pattern indicated that the TLWR was0.59 mm. This value is greater than that of Example 1, indicating thatthere is a greater amount of inter-color bleed and lower resolution. TheCD was 1.33, which is slightly greater than Example 1, but less than theCDs of C3 and C4, indicating that some the ink is being drawn into thepores away from the surface but slightly less than Example 1. Thus, theorientation imposed on this sample as compared to Example 1 generates apore system that does not transfer the ink away from the surface quicklyenough to maintain high resolution and low inter-color bleed. Indeed,immediately after printing, the surface of the film was significantlywetter than that of Example 1.

Example 3

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with inorganic filler, and a terpolymer of ethylene/vinylacetate/carbon monoxide.

Preparation: A sample was compounded and pressed in a similar manner toExample 1 except that it contained 40 weight % polypropylene homopolymer(FINA 3374 available from Atofina Inc., Houston, Tex.) with 40 weight %calcium metasilicate (wollastonite Micronite grade 800H available fromFibertec Inc., Bridgewater, Mass.) and 20 weight % of a terpolymer ofethylene/vinyl acetate/carbon monoxide (ELVALOY 741 available fromDuPont Packaging and Industrial Polymers, Wilmington, Del.). The densityof the resulting pressed sheet was 1.26 g/cm³, and the thickness wasapproximately 1 mm. The pressed sheet was stretched in the same manneras Example 1 with a final biaxial stretch of 3.5×3.5 (MD×TD) asdetermined by Test Method 1. The resulting oriented film had a thicknessof approximately 0.23 mm and a density of 0.37 g/cm³, indicating a voidcontent of 71% as per Test Method 2. SEM image of the surface of theoriented film indicates that the surface is porous.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was somewhat non-uniform with some mottling evident.Evaluation of the test pattern indicated that the TLWR was 0.67 mm. Thisvalue is greater than that of Examples 1 and 2, indicating that there isa greater amount of inter-color bleeding and lower resolution. The CDwas 1.19, which is less than Examples 1 and 2. This is likely due to themottled ink coverage leading to small regions of entrapped white space.The poorer ink coverage and greater amount of bleeding may be attributedto the large size of the surface pores for this sample in comparison toExamples 1 and 2. SEM reveals that the surface pores are several timeslarger in diameter for this sample than the previous two. Thus, althoughthis sample has been stretched in the same fashion as Example 1 and hasthe same print additive, the higher content of the ELVALOY 741 in thefilm resulted in a distinctly different pore structure and a distinctlypoorer image quality. Thus, there is a complex interaction between theamount of print additive, the resulting pore structure and interactionwith the ink that must be carefully optimized to generate the bestinkjet printing quality.

Example 4

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film substrate comprised of a blend ofpolypropylene with an inorganic filler and an ethylene and vinyl acetatecopolymer resin.

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 40 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.) and 20 weight % of anethylene and vinyl acetate copolymer resin (ELVAX 240 available fromDuPont Packaging and Industrial Polymers, Wilmington, Del.). The densityof the resulting pressed sheet was 1.25 g/cm³ and the thickness wasapproximately 1 mm. The pressed sheet was stretched in the same manneras Example 1 with a final biaxial stretch of 3.5×3.5 (MD×TD) asdetermined by Test Method 1. The resulting oriented film had a thicknessof approximately 0.13 mm and a density of 0.45 g/cm³, indicating a voidcontent of 65% as per Test Method 2. SEM images of the surface andcross-section of the oriented film indicate that the film is highlyvoided with a surface that is very porous. In comparison to Example 1,the interior of the film is composed of thicker layers of polymer thatare more widely spaced apart, and the surface contains a distribution ofpores that vary in size much more broadly than in Example 1. Indeed,some are greater than 200 μm in diameter.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was very non-uniform with a significant amount of mottlingevident. Because of the high degree of inter-color bleeding, the testpattern was not resolvable, and it was not possible to measure a TLWR.Although the ink coverage was non-uniform, it was possible to measure asolid block CD in certain regions of 1.06. This low value is likely dueto both the mottled ink coverage leading to small regions of entrappedwhite space and the large pores that allow the ink to penetrate quicklybelow the surface. Thus, although this sample has been stretched in thesame fashion as Example 1 and has a print additive that has a goodaffinity for the ink (cf. Table 1), the pore structure was not optimalfor inkjet printing, and the image quality was significantly lower. Mostlikely this is due to the presence of surface pores that are larger insize than the diameter of an ideal dot of ink (ca. 65 μm based on a 70μL droplet) immediately after it has been jetted from the print head andlanded on the surface. It was noted that the ink was dry immediatelyafter printing.

Example 5

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler and an ethylene and a styrenicthermoplastic elastomer.

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 40 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.) and 20 weight % of astyrenic thermoplastic elastomer (KRATON D-1107 available from KratonPolymers, Houston, Tex.). The density of the resulting pressed sheet was1.25 g/cm³, and the thickness was approximately 1 mm. The pressed sheetwas stretched in the same manner as Example 1 with a final biaxialstretch of 3.5×3.5 (MD×TD) as determined by Test Method 1. The resultingoriented film had a thickness of approximately 0.15 mm and a density of0.48 g/cm³, indicating a void content of 62% as per Test Method 2. SEMimages of the surface of the oriented film indicate that the film'ssurface is very porous. In comparison to Example 1, the surface containssignificantly larger pores, some greater than 150 μm in diameter.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was very non-uniform with a significant amount of mottlingevident. Because of the high degree of inter-color bleeding, the testpattern was not resolvable, and it was not possible to measure a TLWR.Although the ink coverage was non-uniform, it was possible to measure asolid block CD in certain regions of 0.60. This low value is likely dueto a several of factors. As with Example 4, the mottled ink coverage andlarge pore size tend to decrease CD, but the very high affinity of theink for the Kraton Resin (cf. Table 2) tended to make the CD drop evenlower in this case. Thus, as with Example 4 the pore structure was notoptimal for inkjet printing. However, the choice of print additive madethe CD even lower. It was noted that the ink was dry immediately afterprinting.

In addition to inkjet printing, a portion of this sample was alsoprinted upon via traditional screen-printing for comparison. The samplewas printed using a screen printing station (CAMEO 2455, available fromAmerican Screen Printing Equipment Company, Chicago Ill.) withcommercially available black ink (Scotchcal 9705, available from 3MCompany, Saint Paul, Minn.) and a 380 mesh screen. After printing, theink was cured in a UV curing station (Model CV-38-T3, available fromAmerican Ultraviolet Company, Murray Hill, N.J.) consisting of two banksof lamps with a net energy exposure of 180 mJ/cm². In contrast to inkjetprinting, the image quality of the screen-printed sample was relativelyhigh with no bleeding, high resolution and a color density of 1.33.

Example 6

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler and poly(methyl methacrylate).

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 50 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.) and 10 weight % ofpoly(methyl methacrylate) (CP-80 Clear, available from Ineos AcrylicsInc., Cordova, Tenn.). The density of the resulting pressed sheet was1.27 g/cm³, and the thickness was approximately 1 mm. The pressed sheetwas stretched in the same manner as Example 1 with a final biaxialstretch of 3.5×3.5 (MD×TD) as determined by Test Method 1. The resultingoriented film had a thickness of approximately 0.25 mm and a density of0.31 g/cm³, indicating a void content of 76% as per Test Method 2.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was somewhat non-uniform with some mottling evident.Evaluation of the test pattern indicated that the TLWR was 0.67 mm. Thisvalue is greater than that of Example 1, indicating that there is agreater amount of inter-color bleeding and lower resolution. The CD was1.23, helping the overall image quality to approach a satisfactorylevel. It was observed that the sample was slightly wet immediatelyafter printing.

Example 7

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler and poly(isobutyl methacrylate).

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 50 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.) and 10 weight % ofpoly(isobutyl methacrylate) (PARALOID B-67 available from Rohm and Haas,Co., Philadelphia, Pa.). The density of the resulting pressed sheet was1.26 g/cm³, and the thickness was approximately 1 mm. The pressed sheetwas stretched in the same manner as Example 1 with a final biaxialstretch of 3.5×3.5 (MD×TD) as determined by Test Method 1. The resultingoriented film had a thickness of approximately 0.25 mm and a density of0.41 g/cm³, indicating a void content of 67% as per Test Method 2.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was uniform with no significant mottling evident.Evaluation of the test pattern indicated that the TLWR was 0.67 mm. Thisvalue is greater than that of Example 1, indicating that there is agreater amount of inter-color bleeding and lower resolution. The CD was1.15. With respect to Example 6, which contains the same weight % of adifferent methacrylate resin, it is noteworthy that the differencebetween their relative IT #s (Table 2) is reflected in the differencesin the ink uniformity on their surfaces, i.e. Example 6 is more mottled.It was observed that the sample was slightly wet immediately afterprinting.

Example 8

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler and styrene acrylonitrilecopolymer.

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 50 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.) and 10 weight % ofstyrene acrylonitrile copolymer (LURAN 358 N available from BASFCorporation, Mount Olive, N.J.). The density of the resulting pressedsheet was 1.26 g/cm³ and the thickness was approximately 1 mm. Thepressed sheet was stretched in the same manner as Example 1 with a finalbiaxial stretch of 3.5×3.5 (MD×TD) as determined by Test Method 1. Theresulting oriented film had a thickness of approximately 0.15 mm and adensity of 0.34 g/cm³, indicating a void content of 73% as per TestMethod 2. SEM images of the surface of the oriented film indicate thatthe film's surface is very porous. In comparison to Example 1, thesurface contains significantly larger pores, some greater than 150 μm indiameter.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was somewhat non-uniform with a small amount of mottlingevident. Because of the significant degree of inter-color bleeding, thetest pattern was not resolvable, and it was not possible to measure aTLWR. Although the ink coverage was non-uniform, it was possible tomeasure a solid block CD in certain regions of 1.26. Thus, although theCD was relatively high, the large amount of inter-color bleeding andmottled ink coverage made the overall image quality low. These issuesare most likely due to the large size of the surface pores.

Comparative Example C-5

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler and an ethylene octene copolymer.

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 50 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.) and 10 weight % ofethylene octene copolymer (ENGAGE 8200 available from Dow DuPontElastomers L.L.C., Wilmington, Del.). The density of the resultingpressed sheet was 1.23 g/cm³, and the thickness was approximately 1 mm.The pressed sheet was stretched in the same manner as Example 1 with afinal biaxial stretch of 3.5×3.5 (MD×TD) as determined by Test Method 1.The resulting oriented film had a thickness of approximately 0.13 mm anda density of 0.62 g/cm³, indicating a void content of 49% as per TestMethod 2. SEM images of the surface of the oriented film indicate thatthe film's surface is not porous, similar to that of Example C4.Image Quality: The voided film sample was printed upon using the Xaarpiezoelectric inkjet printer as described above. As with example C4, theink coverage on the film surface was very non-uniform with significantmottling and coalescing of the ink. Indeed the test pattern was notresolvable, making it impossible to measure a TLWR. It was, however,possible to measure a solid block CD in certain regions of 1.3, and itwas also observed that the ink was very wet immediately after printing.As with example C4, the poor image quality and slow drying rate are bothresults of the low porosity and low affinity of the ink for thepolypropylene surface. SEM reveals the surface has practically no poreseven though it has been stretched significantly and is almost 50% voids.Apparently, addition of the ethylene/1-octene copolymer at this loadingdoes not produce a porous structure, in contrast to the previousExamples that contain a second resin component. Possibly this is due tothe fact that the ethylene/1-octene copolymer is more miscible with thepolypropylene, making the interfaces between the polymer phases strongersuch that they do not tear apart when the film stretched. It is thistearing apart of the immiscible phases that induces the pore structureto develop in these systems.

Example 9

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler, a terpolymer of ethylene/vinylacetate/carbon monoxide, and poly(isobutyl methacrylate).

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 50 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.), 5 weight % of aterpolymer of ethylene/vinyl acetate/carbon monoxide (ELVALOY 741available from DuPont Packaging and Industrial Polymers, Wilmington,Del.), and 5 weight % of poly(isobutyl methacrylate) (PARALOID B-67available from Rohm and Haas, Co., Philadelphia, Pa.). The density ofthe resulting pressed sheet was 1.27 g/cm³ and the thickness wasapproximately 1 mm. The pressed sheet was stretched in the same manneras Example 1 with a final biaxial stretch of 3.5×3.5 (MD×TD) asdetermined by Test Method 1. The resulting oriented film had a thicknessof approximately 0.23 mm and a density of 0.38 g/cm³, indicating a voidcontent of 70% as per Test Method 2. SEM images of the surface of theoriented film indicates that the film is highly voided with a surfacethat is very porous.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. Similar to Example 1,the ink coverage on the film surface was uniform with no significantmottling. Evaluation of the test pattern indicated that the TLWR was0.50 mm, and the CD was 1.24. These values are identical to Example 1,and indeed, the overall image qualities of the two samples were nearlyequivalent. Comparison of the SEM micrographs indicates that the surfacepore sizes of the two samples were very similar, both generally lessthan 100 μm in diameter. In addition, this sample was dry afterimmediately printing. Thus, by incorporating of a blend of differentresin additives with IT#s indicative of favorable interactions with theink (cf. Table 2), it is also possible to generate an inkjet printingsubstrate with a good image quality.

In addition to inkjet printing, this sample was also printed upon viatraditional screen-printing for comparison, as described in Example 5.In contrast to inkjet printing, the image quality of the screen-printedsample was relatively high with no bleeding, high resolution and a colordensity of 1.73.

Example 10

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler, a terpolymer of ethylene/vinylacetate/carbon monoxide, and poly(isobutyl methacrylate).

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 40 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % calcium metasilicate (wollastonite Micronite grade 800Havailable from Fibertec Inc., Bridgewater, Mass.), 10 weight % of aterpolymer of ethylene/vinyl acetate/carbon monoxide (ELVALOY 741available from DuPont Packaging and Industrial Polymers, Wilmington,Del.), and 10 weight % of poly(isobutyl methacrylate) (PARALOID B-67available from Rohm and Haas, Co., Philadelphia, Pa.). The density ofthe resulting pressed sheet was 1.28 g/cm³, and the thickness wasapproximately 1 mm. The pressed sheet was stretched in the same manneras described in Example 1 with a final biaxial stretch of 3.5×3.5(MD×TD) as determined by Test Method 1. The resulting oriented film hada thickness of approximately 0.23 mm and a density of 0.43 g/cm³,indicating a void content of 66% as per Test Method 2. SEM images of thesurface of the oriented film indicates that the film is highly voidedwith a surface that is very porous.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was fairly uniform with a slight degree of mottlingevident. Evaluation of the test pattern indicated that the TLWR was 0.67mm, and the CD was 1.21. Thus, although the CD of this sample is closeto that of Example 9, the resolution, inter-color bleeding, and inkcoverage are distinctly poorer. In addition, this sample was dryimmediately after printing. These observations are likely due to thelarger pore sizes on the surface of this substrate; SEM shows some poresas large as 200 μm. This again is indication that the image quality isstrongly dependent on both the selection of print additives used tomaintain high color density and on the processing to generate a porestructure that takes ink away from the surface but does not interferewith resolution, ink coverage, or induce bleeding.

In addition to inkjet printing, a portion of this sample was alsoprinted upon via traditional screen-printing for comparison, asdescribed in Example 5. In contrast to inkjet printing, the imagequality of the screen-printed sample was better with no bleeding, highresolution and a color density of 1.55. It should be noted that althoughthere were slight differences in the CDs of the three screen printedsamples (Examples 5, 9, and 10), their overall image qualities were verysimilar. All three samples provided very good resolution, and thedifference in CD between Examples 9 (the highest CD) and 5 (the lowestCD) was only 30%. In contrast, the overall image qualities of thecorresponding samples printed by inkjet printing were significantlydifferent. Example 9 had a far better IQ than Example 5. Its CD, forexample, was 206% higher and it had a TLWR of 0.50 mm. Whereas, Example5 had such a large amount of intercolor bleed that no TLWR wasresolvable using our test pattern. Example 10 fell between the other twosamples in both image quality measurements. Thus, printing viapiezoelectric inkjet printing is a much more demanding method, and itssubstrates must be more carefully prepared than for other printingmethods such as screen printing.

Finally, a series of SEM micrographs were taken of the surface of thissample and its precursor pressed sheet after they had been exposed toruthenium tetroxide (RuO₄) in order to selectively stain the additivesin the film. FIG. 3 shows the surface of the oriented, cast film.Because the RuO₄ selectively stains double bonds, which are present inthe additive resins and not in polypropylene, it generates contrastbetween the different resins. The light regions denote the presence ofthe additives resins (ELVALOY 741 and PARALOID B-67) on the surface ofthe pressed sheet. In FIG. 3 this contrast is still evident, indicatingthat the resins remain on the surface as separate phases from thepolypropylene.

Comparative Example C6

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a cast sheet comprised of a blend of polypropylene with aninorganic filler, a terpolymer of ethylene/vinyl acetate/carbonmonoxide, and poly(isobutyl methacrylate).

Sample Preparation: A sample containing 40 weight % polypropylenehomopolymer (FINA 3376 available from Atofina, Inc., Houston, Tex.), 40weight % calcium metasilicate (wollastonite Micronite 800H availablefrom Fibertec Inc., Bridgewater, Mass.), 10 weight % of a terpolymer ofethylene/vinyl acetate/carbon monoxide (ELVALOY® 741 available fromDuPont Packaging and Industrial Polymers, Wilmington, Del.), and 10weight % of poly(isobutyl methacrylate) (Parloid® B-67 available fromRohm and Haas Co., Philidelphia, Pa.) was compounded and cast using a 25mm twin screw extruder (available from Werner & Pfleiderer GmbH,Stuttgart, Germany) operated at 193° C., equipped with a die which wasoperated at 200° C. The cast material was quenched on a chrome wheeloperated at 38° C. The line was run at 4.6 m/min. The resulting castsheet had a thickness of 0.53 mm and a density of 1.23 g/cm³.Image Quality: The cast sheet was printed upon using a Xaarpiezoelectric inkjet printhead described above. Similar to Example 1,the ink coverage on the film surface was non-uniform with a slightdegree of mottling evident. Because of large amount of inter-colorbleeding, the test pattern was not resolvable, making it impossible tomeasure a TLWR. It was, however, possible to measure a solid block CD incertain regions of 1.47. It was also observed that the ink was extremelywet immediately after printing and did not dry for several hoursafterwards. Thus, it is evident that although this sample contained thesame additives as in Example 9 and 10, its lack of porosity resulted invery poor image quality due to the large degree of inter-color bleeding.

Example 11

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler, a terpolymer of ethylene/vinylacetate/carbon monoxide, and poly(isobutyl methacrylate).

Sample Preparation: A sheet was compounded and cast in the same manneras described in Example C6 except that it was 1 mm in thickness andhaving a density of 1.28 g/cm³. This cast sheet was orientedsequentially using a length orienter (LO) and tenter (TD) (bothmanufactured by Brückner Maschinenbau GmbH, Siegsdorf, Germany) at adraw ratio of 2.0 in MD and 3.75 in TD as determined by Test Method 1.The final biaxial stretch was, therefore, 2.0×3.75 (MD×TD). Thetemperatures of the LO rolls were each 90° C. and the tenter zones wereall heated to 159° C. The resulting oriented film had a thickness ofapproximately 0.25 mm and a density of 0.45 g/cm³, indicating a voidcontent of 65% as per Test Method 2. FIG. 4 shows SEM images of thesurface of the oriented film, indicating that the film is highly voidedwith a surface that is very porous.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. Similar to Example 10(which has the same composition but was prepared in a different manner),the ink coverage on the film surface was fairly uniform with a slightdegree of mottling evident. Evaluation of the test pattern indicatedthat the TLWR was 0.59 mm, and the CD was 1. 15. Thus, although the CDof this sample was slightly lower than Example 10, the resolution,inter-color bleeding, and ink coverage were distinctly better. It wasalso observed that this sample was dry after immediately printing. Thedifferences between this sample and Example 10 are again most likely dueto the differences in pore structure resulting from the differentorientation processing. This sample was oriented in a sequential manner,whereas Example 10 was oriented in a simultaneous manner. Indeed,comparing FIGS. 3 and 4, it is apparent that there are different porestructures present. This sample has a more fibrous surface that is aresult of its initial MD orientation. The final result is that thisexample has an overall image quality that is notably better than that ofExample 10.

Comparative Example C-7

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler, a terpolymer of ethylene/vinylacetate/carbon monoxide, and poly(isobutyl methacrylate) laminated to anadhesive liner.

Sample Preparation: A sheet was compounded and cast in the same manneras described in Example C-6, having a density of 1.28 g/cm³ and athickness of 0.5 mm. The cast sheet was stretched in a similar manner asthat described in Example 1 except at a temperature of 155° C. and witha final biaxial stretch of 3.0×3.0 (MD×TD) as determined by TestMethod 1. The resulting oriented film had a thickness of approximately0.11 mm and a density of 1.0 g/cm³, indicating a void content of 22% asper Test Method 2. SEM images of the surface of the oriented filmindicates that the film is not very porous. The oriented film waslaminated onto an acrylic-based adhesive coated at 25 g/m² onto apolyethylene coated paper liner treated with a cured silicone releasesystem.Image Quality: A graphical image was printed upon the surface using anArizona Sign Printer (Model SP-62 available from Gretag Imaging Inc.,Holyoke, Mass.) using the Scotchcal™ 3700 series inks described above inaddition to light magenta (3781) and light cyan (3786) using a 63% inklay down. The graphic was observed to have a fairly poor image quality,as it was blurry, mottled and faded. The poor image quality is likelydue to the lack of porosity on the surface that allowed the ink to bleedon the surface.

Example 12

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler, a terpolymer of ethylene/vinylacetate/carbon monoxide, and poly(isobutyl methacrylate) laminated to anadhesive liner.

Sample Preparation: An oriented film was prepared in an identical mannerto that described in Example 11 and laminated onto an adhesive liner inthe same manner as described in Example 13. The oriented film had athickness of approximately 0.45 mm and a density of 0.43 g/cm³,indicating a void content of 66% as per Test Method 2.Image Quality: A graphical image was printed upon the surface in thesame manner as described in Comparative Example C-7; however, its imagequality was substantially superior to that of Example C-7. Ink coveragewas significantly more vibrant and uniform, and the image was notblurry. The SEM of the equivalent material (described in Example 10)shows the surface of this sample is much more porous than that ofComparative Example C-7. Thus, it is this surface porosity inconjunction with the added resins that allow the image quality of thismaterial to be significantly better than that of Comparative ExampleC-7.

Example 13

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler, a terpolymer of ethylene/vinylacetate/carbon monoxide, and poly(isobutyl methacrylate).

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 40 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % precipitated calcium carbonate (Vicality™ Albaglos™ PCCavailable from Specialty Minerals, Bethlehem, Pa.), 10 weight % of aterpolymer of ethylene/vinyl acetate/carbon monoxide (ELVALOY™ 741available from DuPont Packaging and Industrial Polymers, Wilmington,Del.), and 10 weight % of poly(isobutyl methacrylate) (PARALOID™ B-67available from Rohm and Haas, Co., Philadelphia, Pa.). The density ofthe resulting pressed sheet was 1.24 g/cm³ and the thickness wasapproximately 1 mm. The pressed sheet was stretched in the same manneras Example 1 with a final biaxial stretch of 3.5×3.5 (MD×TD) asdetermined by Test Method 1. The resulting oriented film had a thicknessof approximately 0.13 mm and a density of 0.98 g/cm³, indicating a voidcontent of 21% as per Test Method 2. SEM images of the surface and crosssection of the oriented film, indicates that the film is voided with asurface that is porous.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was non-uniform with a significant amount of mottlingevident. There was also a high degree of inter-color bleeding that madethe test pattern not resolvable, and it was not possible to measure aTLWR. Although the ink coverage was non-uniform, it was possible tomeasure a solid block CD in certain regions of 1.16. The poor imagequality is likely due to large pore size and low void content. It wasalso noted that the ink was still wet immediately after printing. Thus,although this sample has been stretched in the same fashion as Example10 and has the exact same print additives, the pore structure was notoptimal for inkjet printing, resulting in an image quality that wassignificantly lower. The only difference between this sample and Example10 is the type of particulate filler used. In this case, the particle isCaCO₃ having a median particle size of 0.8 μm. In the next two examples,the results when using two additional different types of calciumcarbonate fillers are described. A comparison of the effects of thesedifferent particle types is made below in the discussion of Example 15.

Example 14

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler, a terpolymer of ethylene/vinylacetate/carbon monoxide, and poly(isobutyl methacrylate).

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 40 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % precipitated calcium carbonate (CALESSENCE™ 300 PCCavailable from Specialty Minerals, Bethlehem, Pa.), 10 weight % of aterpolymer of ethylene/vinyl acetate/carbon monoxide (ELVALOY™ 741available from DuPont Packaging and Industrial Polymers, Wilmington,Del.), and 10 weight % of poly(isobutyl methacrylate) (PARALOID™ B-67available from Rohm and Haas, Co., Philadelphia, Pa.). The density ofthe resulting pressed sheet was 1.21 g/cm³, and the thickness wasapproximately 1 mm. The pressed sheet was stretched in the same manneras Example 1 with a final biaxial stretch of 3.5×3.5 (MD×TD) asdetermined by Test Method 1. The resulting oriented film had a thicknessof approximately 0.15 mm and a density of 0.76 g/cm³, indicating a voidcontent of 37% as per Test Method 2. SEM images of the surface and crosssection of the oriented film indicates that the film is voided with asurface that is porous.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was non-uniform with a significant amount of mottlingevident. There was also a high degree of inter-color bleeding that madethe test pattern not resolvable, and it was not possible to measure aTLWR. Although the ink coverage was non-uniform, it was possible tomeasure a solid block CD in certain regions of 1.10. It was observedthat the sample was dry immediately after printing. As with Example 13,this sample was stretched in the same fashion as Example 10 and has theexact same print additives, but the pore structure was not optimal forinkjet printing, resulting in an image quality that was significantlylower. Again, the only difference between this sample and Example 10 isthe type of particulate filler used. In this case, the particle is CaCO₃having a median particle size of 3 μm.

Example 15

This example is a demonstration of solvent-based piezoelectric inkjetprinting on a biaxially oriented film comprised of a blend ofpolypropylene with an inorganic filler, a terpolymer of ethylene/vinylacetate/carbon monoxide, and poly(isobutyl methacrylate).

Sample Preparation: A sample was compounded and pressed in a similarmanner to Example 1 except that it contained 40 weight % polypropylenehomopolymer (FINA 3374 available from Atofina Inc., Houston, Tex.) with40 weight % surface treated fine ground limestone (Hi-Pflex™ 100 PCCavailable from Specialty Minerals, Bethlehem, Pa.), 10 weight % of aterpolymer of ethylene/vinyl acetate/carbon monoxide (ELVALOY™ 741available from DuPont Packaging and Industrial Polymers, Wilmington,Del.), and 10 weight % of poly(isobutyl methacrylate) (PARALOID™ B-67available from Rohm and Haas, Co., Philadelphia, Pa.). The density ofthe resulting pressed sheet was 1.28 g/cm³, and the thickness wasapproximately 1 mm. The pressed sheet was stretched in the same manneras Example 1 with a final biaxial stretch of 3.5×3.5 (MD×TD) asdetermined by Test Method 1. The resulting oriented film had a thicknessof approximately 0.17 mm and a density of 0.81 g/cm³, indicating a voidcontent of 37% as per Test Method 2 SEM images of the surface and crosssection of the oriented film indicates that the film is voided with asurface that is porous.Image Quality: The porous film was printed upon using a Xaarpiezoelectric inkjet printhead described above. The ink coverage on thefilm surface was fairly uniform with a minor amount of mottling evident.Evaluation of the test pattern indicated that the TLWR was 0.50 mm, andthe CD was 1.13. It was observed that this sample was wet immediatelyafter printing. In contrast to Examples 13 and 14, this sample manifestsan overall image quality that is nearly as high as that of Example 10.The SEM images show the surface pores are significantly smaller thanExamples 13 and 14, and the interior appears more uniformly voided.Thus, the pore structure generated in this sample was far more optimalfor inkjet printing than Examples 13 and 14, but somewhat less than thatof Example 10.

The key difference between each of these samples is the type ofparticulate filler used to induce voiding upon stretching. In thissample, the particles are limestone ground to an average size of 3.5 μmthat has been surface treated with stearic acid at a level of 1%. Thefiller particle used in Example 10 was calcium metasilicate that wassurface treated with phenyl ethoxy silane, having an average length of22 um and a diameter of 3 microns. Thus it is an acicular (needle-like)particle. Table 3 summarizes the types of fillers used in Examples 10,13, 14, and 15. Comparing the results for these with the correspondingparticle types used suggests that particle size may not be the primaryfactor in choosing the particle type. Examples 14 and 15 containedparticles of nearly the same size, but after stretching they resulted insubstantially different films. Noting that both Examples 10 and 15 weresurface coated, it appears that an important factor in selecting aparticle type is that it is coated with a dispersing agent to preventthe particles from agglomerating together.

TABLE 3 Characteristics of Various Inorganic Particulate Fillers FillerType Particle Size (μm) Coating Calessence 300 PCC 3.0 none Hi-Pflex 1003.5 1% stearic acid Micronite 800H wollastonite 22 × 3 phenyl ethoxysilane Vicality Albaglos PCC 0.8 noneSummary:

A summary of the examples described above is presented in Table 4. Basedon these examples, it is apparent that preparation of an orientedpolyolefin-based substrate for piezoelectric inkjet is not a trivialtask. As Examples 5, 9, and 10 indicate, materials that are nearlyequivalent when printed upon via other methods such as screen printingmay have vastly different image qualities when printed by inkjetprinting. The examples described above also highlight the key parametersthat must be controlled in order to generate a biaxially orientedpolyolefin-based substrate that will be suitable for solvent-basedinkjet printing.

The final film should be sufficiently porous to minimize inter-color inkbleed, but the surface pores should be small enough such that they donot adversely affect the spreading of ink drops on the surface. Thispore structure may be varied to some extent by changing the stretchingconditions (draw ratios and temperature). To prevent the ink from beingdrawn by capillary forces away from the surface, resulting in low CD, itis also necessary to include additive resins into the film that havesufficient affinity for the ink to hold it near the surface. Theseadditives are also responsible for inducing the porosity within thefilm, as they should be sufficiently immiscible with the polyolefinmatrix that upon stretching they disengage from the polypropylene andgenerate fissures within the striated layers and especially on thesurface.

For each different type of ink, the optimal additive resin may vary. Tohelp narrow the range of additives, one may utilize the simple IT # testdescribed in Test Method 4.

Incorporation of inorganic filler particulates also plays an importantrole in determining the printability of the resulting film. The fillerparticles generate the internal voiding during stretching that providethe necessary volume for holding the ink once it is drawn away from thesurface. In addition, the voiding within the film makes it white andopaque which is important for most imaging films. It appears thatdispersal of the filler so that agglomerates do not form improves thevoid structure throughout the film and correspondingly the imagequality.

Finally, it is important to note that these factors are strongly coupledin how they impact the final imageability of the resulting film suchthat a change in one factor (e.g. additive resin type) may force one toalso change the other parameters (e.g. processing conditions) in orderto maintain high image quality. Thus, some iterative optimization isinherent to the design of these substrates.

TABLE 4 Summary of image quality measurements, processing, andcompositions of examples % Example CD TLWR MD × TD voids AdditivesFiller Type C1 1.92 0.50 — — — — C2 0.95 0.42 — 40 — — C3 1.73 o.s. 3.5× 3.5 33 — Micronite 800H C4 1.57 o.s. 6.0 × 6.0 58 — Micronite 800H C61.47 o.s. —  0 10% Elvaloy 741 Micronite 800H 10% Paraloid B67  1 1.240.42 3.5 × 3.5 65  5% Elvaloy 741 Micronite 800H  2 1.33 0.59 5.5 × 5.574  5% Elvaloy 741 Micronite 800H  3 1.19 0.67 3.5 × 3.5 71 20% Elvaloy741 Micronite 800H  4 1.06 o.s. 3.5 × 3.5 65 20% Elvax 240 Micronite800H  5 0.60 o.s. 3.5 × 3.5 62 20% Kraton 1107 Micronite 800H  6 1.230.67 3.5 × 3.5 76 10% CP-80 Clear Micronite 800H  7 1.15 0.67 3.5 × 3.567 10% Paraloid B-67 Micronite 800H  8 1.26 o.s. 3.5 × 3.5 73 10% Luran358N Micronite 800H C-5 1.30 o.s. 3.5 × 3.5 49 10% Engage 8200 Micronite800H  9 1.24 0.50 3.5 × 3.5 70  5% Elvaloy 741 5% Micronite 800HParaloid B67 10 1.21 0.67 3.5 × 3.5 66 10% Elvaloy 741 Micronite 800H10% Paraloid B67 11 1.15 0.59  2.0 × 3.75 65 10% Elvaloy 741 Micronite800H 10% Paraloid B67 C-7 n.m. n.m. 3.0 × 3.0 22 10% Elvaloy 741Micronite 800H 10% Paraloid B67 12 n.m. n.m. 3.5 × 3.5 66 10% Elvaloy741 Micronite 800H 10% Paraloid B67 13 1.16 o.s. 3.5 × 3.5 21 10%Elvaloy 741 Vicality 10% Paraloid B67 Albaglos PCC 14 1.10 o.s. 3.5 ×3.5 37 10% Elvaloy 741 Calessence 300 10% Paraloid B67 PCC 15 1.13 0.503.5 × 3.5 37 10% Elvaloy 741 Hi-Pflex 100 10% Paraloid B67 Note: n.m.indicates that a value was not measured for the example o.s. indicatesthat the value was off the scale of the measurement

1. A method of printing with an inkjet printer comprising the step ofjetting a solvent-based inkjet ink onto the image receptor mediumcomprising a porous, biaxially oriented, melt-processed image receptivefilm layer comprising a) an immiscible blend of a semicrystallinepolymer component and an ink absorptive polymer component and b) aninorganic filler.
 2. The method of printing of claim 1 wherein theinkjet ink is a solvent based piezo inkjet ink.
 3. The method ofprinting of claim 1 wherein the ink is jetted using an inkjet printhead.4. The method of printing of claim 1 wherein the semicrystalline polymeris selected from high and low density polyethylene, linear low densitypolyethylene, polypropylene, polyoxymethylene, poly(methyl pentene),poly(ethylene terephthalate), poly(butylene terephthalate), polybutene,and syndiotactic polystyrene.
 5. The method of printing of claim 1wherein the ink absorptive polymer is selected from the group consistingof copolymers of methyl methacrylate with butyl acrylate, butylmethacrylate; isobutyl methacrylate, or isobornyl methacrylate;copolymers of isobutylmethacrylate and butyl methacrylate; butylmethacrylate polymers; vinyl polymers; polystyrene polymers; andcombinations thereof.
 6. The method of printing of claim 1 wherein theink absorptive polymer is selected from the group consisting of acopolymer of methylmethacrylate and butylacrylate, a copolymer ofmethylmethacrylate and isobutylmethacrylate, and combinations thereof.7. The method of claim 1, wherein said ink absorptive polymer componentis present in amounts of 2 to 40 weight %, relative to the weight of theimmiscible polymer blend.
 8. The method of claim 1 wherein inkabsorptive polymer is present in the image receptive layer at a level offrom about 8 to about 20 weight percent, relative to the weight of theimmiscible polymer blend.
 9. The method of claim 1 wherein saidinorganic filler is selected from solid or hollow glass, ceramic ormetal particles, microspheres or beads; zeolite particles; metal oxides;metal, alkali- or alkaline earth carbonates silicates, metasilicates,aluminates or sulfates; kaolin, talc, clays, titanium dioxide or carbonblack.
 10. The method of claim 1 wherein said inorganic filler ispresent in amounts from 25 to 50 weight percent, relative to the weightof the image receptive layer.
 11. The method of claim 1, wherein saidink absorptive polymer component is an ethylene/vinyl acetate/carbonmonoxide terpolymer.
 12. The method of claim 1, wherein said terpolymercomprises 50% to about 80% of ethylene monomer; from about 10% to about30% of vinyl acetate monomer; and from about 4% to about 15% carbonmonoxide monomer.
 13. The method of claim 1, wherein said ink absorptivepolymer has an Inclined Ink Trail Test value of from about 0.75 to 2.0.14. The method of claim 1 wherein said image receptor medium has surfacevoids wherein the average size of the surface voids is from 10 to 70micrometers.
 15. The method of claim 1, wherein the void content is atleast 30%.
 16. The method of claim 1 comprising a continuous phase ofsaid semicrystalline polymer component and a discontinuous phase of saidink absorptive polymer component.
 17. The method of claim 1 wherein thedegree of said biaxially orientation is 5× to 100× total draw ratio. 18.An imaged graphics film prepared by the method of claim 1 having anink-jetted image on a surface of the image receptor medium.
 19. Animaged graphics film of claim 18 having an ink-jetted image on a surfaceof the image receptor medium, and having a color density of at least1.1.